Unsaturated triazine compounds



United States Patent This invention relates to derivatives ofsymmetrical triazine. More specificially, it relates to triazinecompounds of the formula i O C- wherein:

n is an integer having a value of at least 1 and no greater than 3;

A is a bivalent radical selected from the group of O and NR Where R ishydrogen or an alkyl, aryl, or cycloalkyl radical of no more than 12carbon atoms;

Z is a divalent radical selected from the class consisting of divalent,aliphatic, cycloaliphatic and aromatic radicals predominantlyhydrocarbon and having no more than 18 carbon atoms therein;

R" is a radical selected from the class consisting of hydrogen, halogen,and allryl, cycloalkyl and aryl radicals having no more than carbonatoms therein;

In is 0 or i;

Y is a monovalent radical, preferably one selected from the classconsisting of hydrogen, hydrocarbon, halogen, R"O-, R"S-, R N-, whereinR is hydrogen or a hydrocarbon radical preferably of no more than 18carbon atoms.

Compounds of the above structure are referred to hereinafter astriazinyl compounds or triazine monomers. For purposes of simplicity thetrivalent 1,3,5 triazine or symmetrical triazine nucleus is representedherein as C N While the applicants copending application Serial No.764,250, filed September 30, 1958 issued October 2, 1962, as Patent No.3,056,760, of which this application is a continuation-in-part,discloses and claims polymerization products from a broad class oftriazine compounds including certain of the triazine compounds of thisinvention, the compounds of this invention are suited to various othercompositions and uses. For example, they can be used as chemicalintermediates, e.g., by addition of halogen to the ethylenic group togive fire-retardants, inhibitors, rust preventatives, tanning agents,crosslinlring agents for addition polymers, monomers tor condensationpolymers, etc.

The symbol A represents a biradical selected from the class of oxygenand -NR in which R is selected from the class consisting of hydrogen andhydrocarbon radicals, such as: alkyl, aryl, alkaryl, aralkyl,cyloaliphatic, heterocyclic radicals, etc., as Well as theirhalogenated,

cetoxy, alkoxy, aryloxy, alkaryloxy, aralkoxy, etc., substitutionderivatives, e.g., phenethyl, methyl, ethyl, propyl, butyl, amyl, hexyl,octyl, dodecyl, ethoxyethyl, vinyl, allyl, crotyl, cyclohexyl,cyclohexenyl, phenyl, tolyl, benzyl, naphthyl, pyridyl, chlorophenyl,methoxy phenyl, pentachlorophenyl, acetoxynaphthyl, fluoronaphthyl,ethoxynaphthyl, butyroxphenyl, etc. For reasons of availability andeconomy, R is preferably hydrogen, methyl, or ethyl. I g

3,165,515 Patented Jan. 12, 1965 Typical examples of the group CH =CR"(CR" Preferably, because of the ease of polymerizability, R" is hydrogen,as for example, in CH =CH and CH :CHCH.

R" represents hydrogen or a halogen, e.g., Cl, Br, I or F, or asaturated or unsaturated monovalent hydrocarbon radical, such as thealiphatic, cycloaliphatic, aryl, aliphatic-substituted aryl andaryl-substituted aliphatic, etc. radicals, for example, methyl, ethyl,vinyl, ethynyl, propyl, allyl, propargyl, butyl, methallyl, butenyl,amyl, hexyl, octyl, crotyl, cyclopentyl, cyclopentenyl, cyclohexyl,cyclohexenyl, cycloheptyl, phenyl, diphenyl, Xenyl, napthyl, antracyl,tolyl, Xylyl, ethylphenyl, propylphenyl, isopropylphenyl, allyl phenyl,Z-butenyl-phenyl, propenylphenyl, t-butylphenyl, methylnaphthyl, benzyl,cinnamyl, phenylethyl, phenylpropyl, etc.

in the triazinyl vinyl monomers of this invention Z is a divalenthydrocarbon radical and includes, for example, divalent aliphaticradicals, aromatic radicals, cycloaliphatic radicals, etc., includingvarious combinations of such radicals, such as alkaryl, aralkyl, etc.,including diaryl oxides, diaryl sulfides, diaryl amines, etc., all ofwhich radicals can also have substituents thereon such as chloro,fluoro, alkoxy, aryloxy, acyloxy, etc. groups. Illustrative examples ofdivalent radicals that Z can represent in the above formula are:

The substituent groups such as the alkoxy, aryloxy, acyloxy, alkylamino,arylamino, etc., radicals are advan tageously radicals of no more thanabout ten carbon atoms, such as methoxy, ethoxy, butoxy, pentoxy,oxtoxy, phenylmethoxy, phenylethoxy, acetoxy, propionoxy, butyroxy,valeroxy, capryloxy, benzoxy, phenylacetoxy, toluoxy, etc. Other groups,such as nitroso, nitro, etc., can also be used as substituents on the Zgroup provided they are inert during the preparation and use of thetriazinyl vinylmonomer. The aliphatic group, or that portion of the Zgroup which is aliphatic, can be saturated or unsaturated, e.g., -CHCH:CH;

-CEC; -CH CH=CHCH:CHCH etc. Also, without departing from the spirit ofthis invention, the carbon atoms in the divalent radical, Z, can beinterrupted by an atom other than carbon, e.g.,

etc.

While other hydrocarbon and substituted hydrocarbon groups are alsoeffective as Z groups, the groups indicated above are preferred forreasons of availability and economy.

The triazinyl vinyl compounds of this invention can be written as(M),,(C N (Y) in which M represents the radical containing thepolymerizable group, and the other symbols are as defined above. Wherethe monomer contains only one polymerizable group, soluble, fusiblepolymers can be obtained. When the monomer contains two polymerizablegroups, that is (M) is (M) and the remaining or third group is the sameor different from the M group, insoluble, infusible polymers can beproduced therefrom. When (M) is (M) insoluble, infusible polymers andcopolymers can still be obtained where the Y group is any otherpolymerizable or non-polymerizable monovalent radical.

For example, Y can be hydrogen and alkyl, aryl, aralkyl, alkaryl,cycloaliphatic and heterocyclic groups and their chloro, fluoro, alkoxy,aryloxy, acyloxy derivatives, such as methyl, ethyl, propyl, isopropyl,butyl, octyl, decyl, chloroethyl, fluoropropyl, cycloheXyl, cyclopentyl,phenyl, chlorophenyl, fluorophenyl, Xenyl, naphthyl, tolyl, isopropylphenyl, benzyl, phenethyl, phenyl propyl, acetoxy benzyl, ethoxy propyl,methyl naphthyl, vinyl, allyl, methallyl, allyl phenyl, etc., radicals;Y can also be hydroxyl and the alkoxy and aryloxy radicals derived fromaliphatic, cycloaliphatic, aromatic and heterocyclic hydroxy compoundssuch as methyl alcohol, ethyl alcohol, isopropyl alcohol, butyl alcohol,isobutyl alcohol, decyl alcohol, phenol, the o-, m-, and p-cresols, thexylenols, naphthols, ethylene glycol, methyl glycol ether, butyl glycolether, glycerine, penta erythritol, hydroxy naphthalene, hydroxypyridine, as well as the alkoxy and aryloxy radicals of hydroxy acidsand esters such as lactic acids, ethyl lactate, salicylic acid, methylsalicylate; and in addition Y can be an amino group, NH or the radicalof a monoor disubstituted amino group, for example, the radicals derivedfrom ethyl amine, methyl amine, butyl amine, nonyl 4 amine, dimethylamine, aniline, naphthyl amine, ethanol amine, diethanolamine,diisopropanol amine, methyl aniline, piperidine, amino pyridine,hydrazine, symmetrical dimethyl hydrazine, unsymmetrical dimethylhydrazine, as well as the radicals of the amino-acids, amino-amides,amino-nitriles, specific examples of which are:

-NHCII2C O 0 CH3, N(CHz)5C O 0 011 0712 NHCHzCON(CHa)z, -NHCHCN,NHGGH4CN -NHC5H4NHO C CH:

the radicals of semicarbazide and substituted semicarbazides, such assemicarbazide itself, 4-methyl semicarbazide, etc., as disclosed in myUS Patent No. 2,295,565, issued September 15, 1942; the guanazo radicalwhich is attached to the triazine ring by reacting dicyandiamide with ahydrazino triazine as shown in my US. Patent No. 2,295,567, issuedSeptember 15, 1942; the radicals of urea and substituted ureas, such as--NHCONH CH NHCONH, etc., which may be attached to the triazine ring asshown in my U.S. Patent No. 2,312,688, issued March 2, 1943; radicals ofaminoaryl sulphonamides, e.g.

--NHC H SO NH -NHC H,SO NHCH etc. as shown in my US. Patent No.2,312,697, issued March 2, 1943; radicals of acyl hydrazine andsubstituted hydrazines, such as CH CONHNH- C H CONHNC H C H SO NHNHetc.; radicals of alkylene amines, such as Y can also be thepolymerizable radical of the acrylic, methacrylic, chloroacrylic esteror amide of amine alcohols or dialcohols and diamines, e.g.,

etc.; the radicals of polymerizable aminated or hydroxylated alkylenearyl compounds, for example,

etc.; the radicals of malonic and substituted malonic esters, nitrilesand amides, e.g.,

radical such as n It H I-(O oHm, P(O OH OH=CH;);, -1*(o CH;C|=CH=):etc., or a triazine ring, e.g., (CH NH) C N or through a bridge, such as[(CH N] 2 (C N )NHCH CH NH- (C H NH) (C N )OCH CH O-- (HO) (C N )NHCH CHO- etc., or the group can represent the remainder of the molecule, forexample (M) (C N in compounds of the structure (lVI) (C N )(C N (M) aswell as those structures linked together through carbon atoms, sulfuratoms, oxygen atoms, etc, as for example,

etc.

Thus, it may be seen that a wide variety of modified triazinyl vinylcompounds can be prepared in accordance with the practice of thisinvention and this modification is achieved by the nature of the Yradical, which can represent any monovalent radical. However, the Yradical is preferably hydrogen, hydrocarbon, halogen, RO, R"'S, R"' N,wherein R' is hydrogen or a hydrocarbon radical preferably of no morethan 18 carbon atoms.

When one of the groups attached to the triazinyl ring contains apolymerizable ethylenic group which is not inhibited by the other atomsand groups in the monomer, then a soluble, or fusible, orsoluble-fusible polymer is obtained on polymerizing the monomer. Suchmonomers can also be copolymerized with other monovinyl ormonovinylidene monomers, hereinafter generally referred to as vinylmonomers, such as acrylonitrile, methyl methacrylate, etc., to producemodified thermoplastic compositions. It has now been discovered thatwhen two or more polymerizable groups are attached to the triazine ring,insoluble, infusible, heat resistant, and in many casesself-extinguishing polymerization products are obtained. It has beenfurther discovered that the triazinyl-vinyl monomers of this inventioncan be copolymerized with other monoolefinic and polyolefinic monomersto produce new materials ha ing insolubility, infusibility, and heatresistance and valuable and characteristic properties that make themespecially suitable for use in industry, for example, in molding,laminating, casting, coating, and adhesive applications, and for otherpurposes.

As disclosed in the aforementioned copending application, homopolymersof the triazinyl vinyl compounds can be produced as well as compositionsof matter comprising an interpolymer (copolymer) or interpolymers of atleast one triazinyl vinyl compound of this invention and at least oneother polymerizable compound containing the structures or groupings,

Various methods can be employed to produce the triazinyl vinyl monomersof this invention. One method of preparing these new monomers compriseseffecting reaction between a halogenated triazine and MH, wherein M isthe radical containing the polymerizabie group as indicated above, whichreaction is represented as follows, in each case using a hydrohalideacceptor such as sodium hydroxide: (C N CI +3MH- (C N (M) +3HCI.

When it is desired to modify the monomer by the presence of a Y group,this can be accomplished by first introducing the M group and thenintroducing the Y groups, for example: (C N )Cl +2MH (M) (C N )Cl+2HCland (M) (C N )Cl}-YH+(M) (C N )Y+HCl; or if the Y group is alreadyattached to the triazine ring, then the M group can be attached, as forexample:

3 a) 2-l- )z( 3 3) or the Y group can be introduced first, beforeintroducing the M group, as for example:

(C N )Cl +YH- Y(C N )Cl +HCl and Y(C N )Cl +2MH Y(C N (M) +2HCl Thereaction can be generalized further by the equation )3-n( 3 3) )n+ )3n(3 3) hi and in the above equations halogen derivatives other than thechloride can also be used, and n, M and Y have the same meaning givenhereinabove. These reactions can be carried out in an anhydrous liquidmedium such as ether, benzene, dioxane, acetone, etc., or in water, orin mixtures of water with water-soluble solvents such as Theseintermediates can be prepared by various methods reported in theliterature for replacing the halogen atoms in halo triazines, such ascyanuric chloride, with various groups such as hydrocarbon groups,alkoxy, aryloxy, substituted amino groups, mercapto, alkylthio, hydroxy,hydrogen, etc. By using the appropriate reagents with suchhalo-triazines, the various intermediates desired for preparing thecompounds of this invention can be prepared following procedures taughtin the following references.

For introducing NR' groups:

Thurston et al.: Journ. of American Chemical Soc., 73,

Thurston et al.: Journ. of American Chemical Soc., 73,

Cuthbertson et al.: J. Chem. Soc., 1948, 561;

Diels et al.: Ben, 3191 (1903);

Friedheim: J.A.C.S., 66, 1775 (1944);

Pearlman et al.: J.A.C.S., 70, 3726 (1948).

For introducing hydrocarbon-oxy groups:

Dudley et al.: J.A.C.S., 73, 2986 (1951); Diels et al.: Ben, 36, 3191(1903); Hoffman: Ben, 19, 2061 (1886); DAlelio: US. Patent 2,295,562;

Schaefer et al.: J.A.C.S., 73, 2990' (1951).

For introducing hydroxy groups: Klason: J. prakt. Chem., (:2) 34, 152(1886); Finger: 3. prakt. Chem., (2) 75, 103 (1907). For introducingsulfide and mercapto groups: Klason: I. prakt. Chem., (2) 34, 152(1886); Hoffman: Ben, 18, 2196 (1885);

Ciba British Patent 318,275 (1930); DAlelio et al.: US. Patents2,295,561 and 2,295,562.

For introducing hydrocarbon groups: Hentrich et al.: US. Patent1,911,689; Ostrogovich: Chem. Ztg., 36, 738 (1912); Kracker et al: US.Patent 2,273,115.

For introducing hydrogen: Ber: 32, 691 (1899); Hirt et al.: Helv. chim.Acta, 33, 1365 (1950).

Illustrative examples of the MH compounds that can be used in thepreparation of triazine monomers include: HOCHZCH2OCOOOH2CH=CH2HOCHzCH2NHCOOCH2CH=CHz CH3 CH2 CH3 CHROH NC O CHzOH=CHz CHzCHz CHzCH:

NCO O OHzC=CH2 OHQGHZ CH3 HO CHzCaHrCHzNHC O O CH2CH=CH2, Bit) Themonomers of this invention can also be prepared by acylatingintermediates of the formula with an unsaturated ester of chloroformicacid, e.g.,

and

The above reactions are performed in the presence or" a hydrohalideacceptor such as pyridine, tributyl amine, sodium hydroxide, etc., andare usually performed at temperatures below 100 C. and preferably in thepresence of a polymerization inhibitor.

This invention will be more fully described by the following examples.The invention is not to be regarded, however, as restricted in any wayby these examples and they are to serve merely as illustrations. Inthese examples as well as throughout the specification, parts andpercentages shall mean parts by Weight and percentages by weight unlessspecifically provided otherwise.

EXAMPLE I Preparation of Triazine Monomers HOC To a mixture of 26 partsof tris(hydroxyethyl)melamine, C N (NHCH CH OH) and 56 parts of tributylamine in 150 parts of water, in a flask equipped with means forrefluxing, is added slowly and with stirring 36 parts of allylchlorocarbonate, ClCOOCH CH CH in 25 parts of acetone. Upon completionof the addition of the chloride, one part of 2,6-ditertiarybutyl-paracresol is added and the mixture refluxed for one hour and allowed tocool to room temperature. The water is then removed by filtration ordecantation. The monomer is washed with water and recrystallized fromacetone-water mixtures. There is obtained (C N (NHCH CH OCOOCH CH=CHUltimate analyses for carbon, hydrogen, nitrogen, and molecular weightdetermination give values of 49.0%, 5.84%, 16.25%, and 508.8respectively, all of which are in close agreement with the theoreticalvalues. Substitution of an equivalent amount of r 9)z a 3) z z 2 for thetrihydroxy compound, yields the corresponding monomer,

(C H N(C N (NHCH CH OCOOCH CH CH which, on analyses gives values of55.8% carbon, 7.63% hydrogen, 16.86% nitrogen, and a molecular weight ofn to 492.76, all of which values are in close agreement with thetheoretical values.

When equivalent quantities of (CH O) (C N (NHCH C'H OH) 2 are used inthe foregoing procedure, there is obtained (CI-I 0) (C N (NHCH CH OCCOCH CH=CH 2 which, on analyses gives values of 48.26% carbon, 5.55%hydrogen, 17.49% nitrogen, and a molecular weight of 553.6, all or"which values are in close agreement with the theoretical values. The useof CH :CHCH O (C N (NHCH CH CH OH 2 in the above procedure yields (NHCHCH CH OCOOCH CH CH 2 When, instead of the hydroxy compounds, aminocompounds are used in the above procedures, e.g.,

( s s) s 4 2) a the corresponding carbamates are obtained, e.g.,

Altcrnately using the same procedures, the triazine monomers are alsoprepared by using a cyanuric chloride and an hydroxy alkyl carbamicester. For example, (C N )Cl with 3HOCH CH OCOOCH CH:CH in the presenceof a hydrohalide acceptor yields (C N (OCH CH OCOOCH CH CH whereas 3HOCHCH NHCOOCH CH CH yields (C N (OCH CH NHCOOCH CH:CH

and instead of cyanuric chloride, any dichloride, such as Y(Q N )Cl canbe used to give the corresponding diderivative. Instead of the specificchlorocarbonates mentioned above, other chlorocarbonates, such asOIOOOOH2 E=CHh ClOOOCH-OH=CH2 CH3 lHa etc., can be used to give thecorresponding derivatives.

By these procedures, various triazine monomers of this invention areprepared, including those which have the following formulas:

The compounds of this invention can also be used as intermediates forthe preparation of new compounds which have utility other than in thepreparation of polymers. As an example these compounds can behalogenated to produce the chloro or bromo derivatives, etc., asillustrated by the reaction conducted, for example, in carbontetrachloride:

01130 (lJaN3O oHzoHioooooH2oH=oH2+BH CHaO CsNaO CHzCHzO CO CHzOHBrOHzBrWhen the monomer has 2 or 3 unsaturated groups the halogenation can belimited by using the appropriate stoichiometric amount of halogen so asto leave one or two such unsaturated groups and give a product which canbe polymerized, such as O1o3N3o omomooooomoHclomol o OH2CH2O c0 0CH2CH=CH and CH CHCH OOCOCH CH OC N (OCH CH OCOOCH CHBrCI-l l3r) 2Polymers and copolymers prepared from such compounds have built-in flameresistance. The corresponding compounds in which the unsaturation hasbeen completely halogenated can be used as modifiers for polymers togive plasticity and improve their flame resistance.

Other typical halogenated compounds of this invention are:

C3N3(O 011201320 00 o CHQCHBICHQBUQ CHzOH=CHzOOCOCH2CH2C N3 CH2OH2OCOOCHCHCICHZODZ CsNsNHCHzCHzNHC O O CH2CH=CH2 ClC3N3O ofiHio COOCH CH=OHz;etc.

0 00540 O O O CH2CHC1CH2C1 The unsaturated compounds or" this inventioncan also be epoxidized with H 0 and an acid according to wel knownprocedures to give compounds such as C1CaN3(O CsH4OCOOCH CE\ \/CH2)2C1CsN3-O 001140 0 O O CH2CH=CHz 0 onno o 0 0 omoru-orn wherein:

n is an integer having a value of at least 1 and no more than 3;

A is selected from the class consisting of O and NR, wherein R is of nomore than 12 carbon atoms and is selected from the group consisting ofalkyl, aryl having benzene nuclei, and cycloalkyl having 5-7 carbonatoms in the cyclic ring; has no more than 18 carbon atoms and isselected from the class consisting of alkylene, cyclohexylene,alkenylene, phenylene, naphthylene, diphenylene, di phenyleneoxide,diphenylenesulfide, and diphenyleneamine radicals and derivativesthereof having only one derivative group and said derivative group isselected from the class consisting of ehloro, fluoro, alkoxy, aryloxyhaving benzene nuclei, cyclohexyloxy, cyclohexenyloxy, alkenoxy andhydrocarbon carboxylic acyloxy groups;

R" is selected from the class of hydrogen, halogen and hydrocarbon of nomore than 10 carbon atoms;

m is an integer having a value of at least 0 and no more than 1;

Y has no more than 18 carbon atoms and is selected from the classconsisting of hydrogen, hydrocarbon, halogen, OR", NR"' AH, alkenyl,alkyl, aryl of benzene nuclei, cyclohexyl, cyclopentyl and amino; and

R is selected from the class consisting of hydrogen and hydrocarbonhaving no more than 8 carbon atoms.

2. The triazine compound of the formula,

C N (NHCH CH OCOOCH CH=CH 3. The triazine compound of the formula,

(C H NC N NHCH CH OCOOCH CH=CH 2 4. The triazine compound of theformula,

CH OC N (NI-ICH CH OCOOCH CH=CH 2 5. The triazine compound of theformula,

6. The triazine compound of the formula,

C N (NHC H NHCOOCH CH CI-h 3 7. The triazine compound of the formula,

C N (OCH CH OCOOCH CH=CH 3 8. The triazine compound of the formula,

C N (OCI-l CH NHCOOCH CH=CH 9. The triazine compound of the formula,

ClC N (NHCH CH OCOOCH CH CH 2 The triazine compound of the formula,

ClC N (NHC H NHC0O CH CH CH 2 The triazine compound of the formula, C N(NHCH CH NHCOOCH CH CH 3 The triazine compound of the formula,

ClC N OCH CH OCOOCH CH=CH 2 The triazine compound of the formula,

Cl C N (OCH CH OCOOCH CH CH The triazine compound of the formula, Cl C NNHCH CH NHCOOCH CH CH The triazine compound of the formula,

l C N NHC H NHCOOCH CH=CH The triazine compound of the formula,

ClO3NaO OHzCHzO C O O CHzCH ClCHzOl O CHzCHrO C O O CHZOH=OH2 17. Thetriazine compound of the formula, References Cited by the Examiner CH:CHCH OOCOCH CH OC N UNITED STATES PATENTS (0CH CH OCOOCH CHBrCI-I Br)18 h r d f h f 1 2,993,877 7/61 DAlelio 2fi0249.5 X T name compo O e 53,056,760 10/62 DAlelio 26Q-248 X C N (OCH CH OCOOCH CHC1CH C1) 19. Thetriazine compound of the formula, IRVING MARCUS Pnmary Exammu' C N (OCHCH OCOOCH CHBrCI- Br) JOHN D. RANDOLPH, NICHOLAS S. RIZZO,

E 1. s 20. The tnazlne compound of the formula, 10 H mm

1. THE TRIAZINE COMPOUND OF THE FORMULA